Process of rendering textiles water repellent



Parana Aug. 12, 1941 PROCESS OF RENDERING TEXTILES WATER REPELLENT Erik Schirm, Dessau, Anhalt, Germany, assignor,

by mesne assignments, to Heberiein Patent 001'- poration, New York, N. Y., a corporation of New York No Drawing. Application June 26, 1937, Serial No. 150,546. In Germany June 30, 1936 I high molecular weight. The invention also in- 8 Claims.

This invention relates to water-repellent fibers, to processes of producing the same and to the novel agents used in such processes.

In acordance with one process of the prior art, cellulose fibers have been rendered water-repellent by treating the same with higher molecular fatty acid chlorides in the presence of acid binding media. Although this process has been of some value, it is not completely satisfactory for the reason that the bond or ester linkage of the fatty acid upon the fibers is easily disturbed and disrupted by the effect of hydrolyzing agents, the result being that the water-proofing effect is lost during washing. Furthermore, the treatment in accordance with this prior process may weaken the fibers and hence may lessen the life of the treated material.

An object of the present invention is to provide processes of treating fibrous materials with water-repellent substances to produce insoluble compounds which are not substantially affected by hydrolyzing agents and therefore which impart substantially permanent water-repellent qualities. A further object is to provide waterrepellent fibrous materials which possess a strength comparable to those of untreated materials.

Broadly considered, the process of the invention relates to the treatment of various types of fibers, including cotton, jute, linen, hemp, various types of artificial silks and wool, to render them water-repellent, which involves treatment with organic compounds containing a carbon-oxygen group characteristic of ethylene oxide, i. e.

and also a higher molecular hydrocarbon group of at least 8 carbon atoms, which impregnate the fibers and, upon treatment as by heating, cause the fibers to become water-repellent.

The hydrocarbon radicals of the said novel treating agents may be either branched or unbranched long chain aliphatic radicals of 8 or more carbon atoms or alicyclic radicals of high molecular weight. In accordance with one embodiment of the invention with respect to such agents, hydrocarbon radicals are connected directly to the group characteristic of ethylene oxide. In accordance with a second embodiment of this phase of the invention, a hydrocarbon radical is joined indirectly to the ethylene oxide v group by means of any one of the multivalent eludes those compounds wherein the higher molecular hydrocarbon radical is joined to the ethylene oxide group through an aromatic ring as well as those joined through an alicyclic ring. Those compounds are also included which contain alkylene groups between the ethylene oxide radical and the above mentioned multivalent elements or atom groups} In accordance with the fiber treatment process of the present invention, the textile or other fibrous material is heated in the presence of the above disclosed agents until water-repellence occurs. The preferred method involves saturation of the fibers with a solution of the treatment agent in a volatile inert solvent and then heating the treated material at an elevated temperature,

which temperature, of course, should not .be sufficiently high to injure the fibers. have been obtained by carrying out the heat treatment under decreased pressure whereby the solvent is evaporated simultaneously during the reaction of the treating agent upon the fibers.

An alternative treatment within the scope of the present invention involves the introduction of the fibers together with the volatile inert liquid into a closed vessel wherein the temperature is raised sufficiently high to bring about reaction. In this case, low boiling solvents may be used. This latter process may be also carried out with the use of higher boiling solvents, in which case the treatment may be effected in an open vessel and the heating continued until the solvent begins to boil. The particular temperatures employed depend upon the nature of the fibers and the water-repellent agent selected. Temperatures in excess of C. are generally required, although the invention is not limited thereto since any temperature which will bring about the action of the agent upon the fiber to produce waterrepellence is considered within the scope of the present invention.

The hereinabove described water-repellent agents may be prepared in many ways, several of which are practical from a commercial or a technical point of view. One suitable method involves the addition or reaction of a hypohalogen acid upon a long chain aliphatic olefine, e. g. cetene or octadecene, or a higher molecular cyclo-olefine, e. g. octahydro-naphthalene, and also upon an allyl alkyl ether, e. g. allyl-cetyl-ether, an allyl dialkyl amine, e. g. allyl-dilauryl-amine, an allyl alkyl sulfone, e. g. allyl-octadecylsulfone or an alkylor alkoxyl-benzene or -naphthalene-sulfon-allyl-amide, e. g. cetyloxy-benzene-sulfonallyl-amide, which compounds contain a higher molecular alkyl radical, the resulting halogen hydrine being subsequently reacted with an alkali hydroxide or an alkali alcoholate. In this man- Good results ner compounds of the following formulas may be obtained:

C gl[33.CTIC1Ig A second method involves the esteriflcation of higher molecular monoalkyl glycerine ethers or -thioethers, e. g. a-tetradecyl-glycerin-ether or its sulfur analog, with sufficient halogen hydracid to esterify one of the OH groups of glycerine ether and subsequently treating theresulting halogen hydrines as described in the foregoing process. In this manner one obtains for example compounds of the following formulas:

A third process by which the agents of the present invention may be produced involves the conversion of epihalogen hydrines with alkali salts of high molecular fatty acids, e. g. stearic acid, mercaptanes, e. g. tetradecylmercaptan or alkyl phenols, e. g. octyl-phenol, yielding compounds of the following tpyes:

A still further process involves the condensation of ketones with high molecular monoor di-chloracetic acid alkyl or cycloalkyl esters or with nitrogen substituted chloracetamides, which reactions are aided by the use of metallic sodium, magnesiumor zinc amalgam, sodium amide or alkali alcoholates, yielding compounds as used in Examples 4 and 5.

Finally a process by which the agents may be produced involves the condensation of high molecular phenacyl-halogenides, e. g. p-octadecyloxyphenacyl-chloride, with aldehydes or ketones, e. g. acetone or benzaldehyde, in the presence of the above named condensation means. A compound obtained according to this process is used in Example 6.

Unlike fibers treated by prior processes, the fibers produced in accordance with the present invention do not lose their water-repellent properties upon washing even though the washing operation be repeated many times. Theoretically this quality is apparently attributable to the fact that Example 1 Cotton fabric is introduced into a solution composed of 5 grams of cetene oxide-1 and one liter of benzine. rated, the excess of the solution is squeezed off or extracted through the use of a centrifuge. Then the fabric is heated to a temperature of 150 C. for a period of 20 minutes.

This example indicates the suitablity of compounds of the general formula wherein at least one of the R groups is an alkyl group of higher molecular weight, the remainder being hydrogen atoms.

Example 2 One kilogram of viscose rayon in skein form,

together with a solution of 10 grams of the glycide ester of behenolic acid in 8 liters of benzol, are heated in an autoclave to a temperature of 130 C. for a period of 5 hours. When this treatment is complete and the rayon cooled, the excess solution is removed by centrifuging after which the skeins are dried in conventional manner.

The glycide of behenolic acid is preferably prepared by reacting the sodium salt of the behenolic acid with epichlorhydrine.

Example 3 Wool yarn is saturated with a 1% solution of the glycide ester of montanic acid dissolved in trichlorethylene and then is heated in a partial vacuum to -125 C. until the solvent is substantially completely removed.

The glycide ester of montanic acid may be readily prepared from the sodium salt of the montanic acid and epichlorhydrine.

The two preceding examples illustrate the use and suitability of compounds which possess the general formula II R- wherein R is an alkyl radical of high molecular weight.

Example 4 Cotton threads are mixed with ten times their weight of xylene or of decahydronaphthalene containing in solution 2% of the weight of the weight of the cotton of beta-beta-dimethyl glycidic acid docosylamide. This mixture is then boiled under reflux condensation for a periodof 4 hours. The treated threads are then centrifugedand dried.

The beta-beta-dimethyl glycidic acid docosylamide may be satisfactorily prepared through the action of acetone upon chloracetic acid docosyl- When the fabric is completely satuamide with the aid of metallic sodium or sodium amide in accordance with known procedure.

Example An acetate rayon fabric is saturated with a 5% solution of beta-beta-dimethyl glycidic acid cholesterol ester in decahydronaphthalene and after most of the liquid has been squeezed off, the rayon is heated under a partial vacuum for a period of one hour, to a temperature of 130-140" C.

In the two next preceding examples, other ketones than acetone may be employed, and hence the said processes illustrate the suitability of compounds within the general formula wherein R is a hydrocarbon group of high molecular weight and the R1s are alkyl radicals, which may be of low or higher molecular weight.

Example 6 Viscose rayon is impregnated by'a benzine solution containing one percent of phenyl- (p-octadecyloxybenzoyl-) ethylenoxyde of the formula The impregnated rayon is squeezed oif, dried and heated for two hours in an air bath at 120 C.

The products resulting from the above examples possess durable water-repellent properties and other desirable characteristics mentioned above.

It should be understood that the present invention is not limited to the specific examples hereinbefore given nor to the specific procedures described, but extends to all equivalent materials and processes coming within the terms of the appended claims.

I claim:

I. The process of rendering fibrous materials water-repellent which comprises heating the fibrous material with a compound of high molecular weight containing a hydrocarbon group of at least 8 carbon atoms and a group having an oxygen atom joined to two adjacent linked carbon atoms, at a temperature above about 100 C. until water-repellence occurs in said fibrous material.

2. The process of imparting water-repellent properties to fibers which comprises heating fibers in the presence of an organic compound to a temperature of the order of 100 C. and above, said compound containing a group and also a higher molecular hydrocarbon group of at least 8 carbon atoms in admixture with an inert liquid until water-repellence occurs in said fibers.

3. The process of rendering fibrous materials water-repellent which comprises heating. the fibrous material with an organic compound containing a group and a higher molecular hydrocarbon group wherein at least one of the Rs is an alkyl group of at least 8 carbon atoms and the remainder hydrogen atoms, said heating being conducted at a temperature above about 100 C. until waterrepellence occurs in said fibrous material.

5. The process of rendering fibrous materials water-repellent which comprises heating the fibrous material with a compound of the general formula wherein R is an alkyl radical containing at least 8 carbon atoms, said heating being conducted at a temperature above about 100 C. until waterrepellence occurs in said fibrous material.

6. The process of rendering fibrous materials water-repellent which comprises heating the fibrous material with a compound of the general formula wherein R is a hydrocarbon group containing at least 8 carbon atoms, and the R1s are alkyl radicals, said heating being conducted at a temperature above about 100 C. until water-repellence occurs in said fibrous material.

7. Process of rendering fibrous materials waterrepellent which comprises heating fibers in the presence of an organic compound containing a group and a higher molecular aliphatic group of at least 8 carbon atoms in admixture with a volatile inert liquid at a temperature in excess of about 100 C. until the liquid is evaporated and water-repellence is produced.

8. In the process of imparting water-repellent properties the steps which comprise introducing a fibrous material into a solution of an organic compound containing a group and also a higher molecular hydrocarbon group of at least 8 carbon atoms in an inert liquid,

' removing the fibrous material'when completely saturated, separating 011 the excess solution, and heating at a temperature in excess of about C. until water-repellence is produced.

ERIK BCHIRM. 

